CN101602684A - Threonine manganese and its production and application - Google Patents

Threonine manganese and its production and application Download PDF

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CN101602684A
CN101602684A CNA2009100432983A CN200910043298A CN101602684A CN 101602684 A CN101602684 A CN 101602684A CN A2009100432983 A CNA2009100432983 A CN A2009100432983A CN 200910043298 A CN200910043298 A CN 200910043298A CN 101602684 A CN101602684 A CN 101602684A
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manganese
threonine
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黄逸强
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Changsha Xingjia Biological Engineering Co Ltd
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Abstract

The invention discloses the Threonine huge legendary turtle compound that a kind of name is called threonine manganese, its preparation method may further comprise the steps: with mol ratio is (0.5~1.1): the crystalline hydrate of the vitriol of 2 manganese or the vitriol of manganese and Threonine aqueous solution, under protection of inert gas, react, temperature of reaction is 60~100 ℃, pH value during reaction is 4~8, obtains reaction product behind reaction 0.5~6h; Reaction product is carried out vacuum concentration or used organic solvent extraction, after carrying out drying again, pulverizing, obtain the threonine manganese finished product.Threonine manganese of the present invention can be as the additive of animal-feed, to reach the purpose of effective promotion growth of animal, enhancing animal resistibility and raising food utilization efficiency.

Description

Threonine manganese and its production and application
Technical field
The present invention relates to a kind of fodder additives and preparation method thereof, relate in particular to a kind of amino acid chelate thing and its production and application.
Background technology
Threonine is a kind of important nutrition-fortifying agent, can play the nutritional fortification effect to cereal, cake, milk-product etc.Threonine is the same with tryptophane, also has to recover human-body fatigue, promote the function of growing.Pharmaceutically,, human body skin is had the water holding effect, after oligonucleotide chain combines, can play an important role the protection cytolemma owing to contain hydroxyl in the structure of Threonine; Threonine can also promote the synthetic and Fatty Acid Oxidation of phosphatide in vivo, and its preparation has medicinal efficacies such as the human development of promotion, anti-fatty liveranti-fatty liver, is commonly used for a moiety in the aminoacids complex transfusion.Simultaneously, Threonine is still made efficient low microbiotic hypersensitive---the basic raw material of monobactam.Along with the raising of people's living standard and the continuous development of aquaculture, Threonine has been widely used in and has added pig starter feed, kind pig feed, broiler fodder, prawn feed and eel feed etc. as feed amino acid.Threonine has following characteristics as animal feedstuff additive: can adjust amino acid whose balance in the feed, promote growth of animal; Can improve meat; Can improve the nutritive value of the low animal-feed raw material of amino acid digestibility; Can be used for producing low proteic feed, help to save protein resource; Can reduce the animal-feed raw materials cost; Can reduce ammonia concentration and release rate in nitrogen content in feces of livestock and poultry and the urine, the livestock and poultry house.Threonine is as the common a kind of limiting amino acid of animal, and its content and proportioning directly affect the nutritive value of daily ration and the production performance of livestock and poultry, adds limiting amino acid and can improve efficiency of feed utilization to greatest extent in the animal daily ration.
Trace element manganese is the moiety of enzymes such as arginase in the body, prolinase, pyruvate carboxylase, RNA polymerase, superoxide-dismutase.In addition, mn ion has the action function that activates plurality of enzymes, is the activator of portion water kinases, lytic enzyme, decarboxylase, Starch phosphorylase, coring enzyme etc.Manganese is also relevant with the activity of polysaccharide polymerase and galactotransferase.Manganese can promote the utilization of body to fat, and the function of anti-liver fat sex change is arranged.Manganese still promotes one of important factor of animal gonad development and endocrine function, and is also closely related with hemopoietic function.In addition, manganese can also improve the utilization of body to copper, and copper is another important factor of regulating hematopoiesis.Manganese is as human body and animal trace elements necessary, the inorganic salt form of many at present employing manganese is as fodder additives, animal absorbs must be by the various biological barrier, its specific absorption is low, addition is big, biological value is low, major part is discharged through ight soil, contaminate environment has destruction to the activity of other nutritive ingredients in the feed (as VITAMIN etc.).Also have and adopt solid Threonine and inorganic manganese, but operating process is numerous and diverse, and the solvability of solid Threonine is relatively more difficult jointly as additive.
How better in conjunction with the advantage of above-mentioned nutritive ingredient Threonine and trace element manganese, the complementarity of two kinds of materials can be found full expression in feed, and better promote the synchronous absorption of animal body to above-mentioned two kinds of materials, just become the technical problem that those skilled in the art need to be resolved hurrily.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, a kind of fodder additives threonine manganese that can promote that animal absorbs synchronously to Threonine and trace element manganese is provided, and provide the preparation method of a kind of technology threonine manganese simple, with low cost at this novel substance threonine manganese, also provide a kind of threonine manganese to be applied to method in the animal feedstuff additive simultaneously, to reach effective promotion growth of animal, strengthen the animal resistibility and to improve the purpose of food utilization efficiency.
For solving the problems of the technologies described above, the present invention proposes a kind of Threonine huge legendary turtle compound, it is characterized in that: the name of described Threonine huge legendary turtle compound is called threonine manganese, and its molecular formula is:
Threonine manganese of the present invention is the terra brown powder, and is soluble in water, mainly absorbs by amino acid pinocytosis form in animal body.
The present invention also provides a kind of preparation method of above-mentioned threonine manganese, may further comprise the steps:
(1) with the crystalline hydrate of the vitriol of the vitriol of manganese or manganese and mass concentration is 5%~30% Threonine aqueous solution, the crystalline hydrate of the vitriol of described manganese or the vitriol of manganese and the mol ratio of Threonine are (0.5~1.1): 2, under protection of inert gas, react, temperature of reaction is controlled at 60 ℃~100 ℃, pH value when interpolation sodium hydroxide is kept reaction is 4~8, obtains reaction product behind reaction 0.5~6h;
(2) described reaction product is carried out vacuum concentration until obtaining thick enriched material, perhaps obtain throw out, after more described enriched material or throw out being carried out drying, pulverizing, obtain the threonine manganese finished product with the moisture in the described reaction product of organic solvent extraction.
Above-mentioned preparation method's main reaction formula is:
Figure G2009100432983D00022
Among the above-mentioned preparation method, the vacuum degree control of described vacuum Concentrating Process is at 0.05~0.7kgf/cm 2, thickening temperature is controlled at 50 ℃~90 ℃, and concentration time is 0.5~4h.
Among the above-mentioned preparation method, described organic solvent is ethanol, propyl alcohol or butanols, and the volume ratio of the reaction product of described organic solvent and its extraction is 4~12: 1, and the time of extraction is 2~30min.
Among the above-mentioned preparation method, described exsiccant method is to adopt air-flow wink-dry method or flash distillation wink-dry method, and drying temperature is 80 ℃~160 ℃.
The present invention also provides the application of above-mentioned threonine manganese in the preparation animal feedstuff additive.
With the additive of above-mentioned threonine manganese as the fattening pig feed, add at feed per ton under the situation of 100~200g, can obviously improve the speed of growth of fattening pig, improve its price of deed, help to improve fur outward appearance and the meat of fattening pig.
With the additive of above-mentioned threonine manganese as sow feed, add at feed per ton under the situation of 100~200g, can improve sow reproductive performance and utilize the time limit, keep the normal oestrus cycle, reduce the incidence of miscarriage and dead piglet, increase lactation amount.
With the additive of above-mentioned threonine manganese as the suckling piglet feed, add at feed per ton under the situation of 100~200g, can improve the speed of growth of suckling piglet, preventing osteoporosis is kept the normal growth and the growth of suckling piglet bone.
With the additive of above-mentioned threonine manganese as poultry feed, add at feed per ton under the situation of 300~400g, can promote the poultry growth, improve the utilization ratio of poultry feed, keep the normal growth and the growth of poultry bone; Improve laying rate and egg size, keep shell thickness, reduce the soft shelled egg rate, improve fertility rate of hatching egg and hatching rate.
With the additive of above-mentioned threonine manganese as aquatic animal feed, add at feed per ton under the situation of 100~200g, can strengthen the immunizing power of aquatic animal, reduce the aquatic animal disease incidence.
The addition manner of above-mentioned fodder additives preferably adds with solid form, will make other composition in the feed can the oxidation because of the moisture absorption because add with solid form.
Compared with prior art, the invention has the advantages that: threonine manganese of the present invention is to absorb by the amino acid approach in livestock and poultry alimentary tract, and its absorption rate is fast, and specific absorption improves greatly, and the biological value height can reduce the consumption of fodder additives.Threonine manganese of the present invention also has good promoter action to the micro-element nutrition of improving animal.Threonine manganese of the present invention also can provide the nutrition of Threonine except that satisfying the needs of animal to trace element manganese, so can promote growth of animal, effectively avoid the destruction of inorganic manganese to VITAMIN isoreactivity material in the feed, can significantly improve the utilization ratio of feed.Threonine manganese of the present invention has stable chemical structure as trace mineral supplement, safety non-toxic, nonirritant, and the output of inorganic manganese reduces in the animal excrement, therefore also can protect environment, reduce and pollute.Trace mineral supplement threonine manganese of the present invention can be widely used in (as pig, fowl, aquatic animal etc.) in the various animal-feeds, can significantly improve the growth performance of animal, improves the utilization ratio of feed.The preparation method who the present invention is directed to above-mentioned threonine manganese proposition also has advantages such as technology is simple, easy to operate, with low cost.
Embodiment
Embodiment 1:
A kind of threonine manganese finished product of the present invention; be to prepare: at first open nitrogen valve by following steps; air in the replacement reaction kettle; then under nitrogen protection; get the 41.75g Threonine; put in the reactor that fills the 100g reaction water and fully stir; drop into the manganese sulfate monohydrate of 29.62g again; pH value with 13.88g sodium hydroxide conditioned reaction mixed solution under 93 ℃ of temperature is 5.8; react 1.5h under the condition of normal pressure, then reaction product is used alcohol extraction 15min, the volume ratio of ethanol and reaction product is 8: 1; throw out after the extraction is carried out the air-flow wink-dry under 100 ℃, prepare the threonine manganese finished product after the pulverizing.
Adopt gel filtration chromatography (GB/T 13080.2-2005) that the chelation percent in the reaction product finished product is detected, it is worth all more than 80%.
The above-mentioned fodder additives that makes is made an addition in the brood sow daily ration.Select the Du Luoke multiparity sow of same parity, be divided into three groups (control groups and test one, two group), 10 every group, to breed with 2~3 Du Luoke boars for every group, requirement is finished breeding in a rutting sedson.Wherein add manganous sulfate 200g in the feed per ton of control group, test one group of feed per ton and add threonine manganese 100g, two groups of feeds interpolation threonine manganese 200g per ton of test, test-results sees Table 1.
Table 1: threonine manganese is to the influence of sow reproductive performance
Figure G2009100432983D00041
Annotate: same column shoulder marking-up parent phase expression difference together is remarkable (p>0.05) not; The female expression significant difference (p<0.05) inequality of same column shoulder marking-up.
As can be seen from Table 1, for the young number of nascent work, control group and test group reach significant difference (p<0.05), but to the not influence of nascent litter weight; Along with the variation of feeding time, the young number of the work of its 21 age in days also changes thereupon, and litter weight is not influence still, but survival rate has the difference (p<0.05) of significance; During 42 ages in days, the performance of the young number of living is similar to 21 ages in days, and incubation rate also reaches significant difference (p<0.05).Above result shows: add the test group of threonine manganese, though do not have the ideal of control group at the young number of the work of nascent brood sow, the survival rate in its later stage and incubation rate all reach significant difference, and litter weight also has raising trend.
The feeding experiment that the above-mentioned fodder additives that makes is used for broiler chicks.Select for use 1 age in days health anosis, physically well develop, the normal AA of body weight is for commodity chicks for meat 360 plumages, be divided into control group at random and test one, two group by male and female equalization, principle that body weight is close, every group of 3 repetitions, each repeats 40 plumages, wherein control group feed per ton adds manganous sulfate 400g, tests one group of feed per ton and adds threonine manganese 300g, two groups of feeds interpolation threonine manganese 400g per ton of test.Test-results sees Table 2.
Table 2: threonine manganese is to the influence of broiler chicks growth performance
Group Starting weight g The heavy g in end Day weight gain g Day feed consumption g The material anharmonic ratio The sick sickness rate % of full phase leg
Control group 40.6 a 659.2 a 42.2 a 81.2 a 1.92 a 13.64 a
Test one group 40.5 a 701.2 b 46.2 b 83.1 a 1.80 b 6.9 b
Test two groups 40.7 a 725.7 b 48.3 b 85.3 a 1.77 b 4.7 b
Annotate: same column shoulder marking-up parent phase expression difference together is remarkable (p>0.05) not; The female expression significant difference (p<0.05) inequality of same column shoulder marking-up.
As can be seen from Table 2, control group and test group are not just having difference (p>0.05) on the starting weight, and on end weight, day weight gain, material anharmonic ratio index, all show the difference (p<0.05) of significance, and can effectively improve the incidence of full phase leg disease, difference reaches conspicuous level (p<0.05), to the not influence of daily ration palatability.This test-results shows: the interpolation threonine manganese can effectively improve the sickness rate that the speed of growth, the improvement of chicks for meat are expected anharmonic ratio, raising efficiency of feed utilization, reduced full phase leg disease.
Embodiment 2:
A kind of threonine manganese finished product of the present invention; be to prepare: at first open nitrogen valve by following steps; air in the replacement reaction kettle under nitrogen protection, is got the 348Kg Threonine; put in the reactor that fills the 1000kg reaction water and fully stir; drop into the manganese sulfate monohydrate of 247Kg again, the pH value of keeping reaction mixture with the sodium hydroxide of 115Kg under 93 ℃ of temperature is 5.8, reacts 2h under the condition of normal pressure; then reaction product is delivered in the concentration tank, at 0.5kgf/cm 2Vacuum tightness, 90 ℃ temperature under vacuum concentration 45min, treat product be thick after, with the enriched material blanking, go into dish, under 120 ℃, carry out the flash distillation wink-dry, prepare the threonine manganese finished product after the pulverizing.
Adopt gel filtration chromatography (GB/T 13080.2-2005) that the chelation percent in the reaction product finished product is detected, it is worth all more than 80%.
The above-mentioned fodder additives that makes is used for the aquatic animal feeding experiment.Select for use physique stalwartness, health not to have gift tilapia 270 tails of obvious damage, be divided into two test group and a control group at random, every group of 3 repetitions, each repeats 30 tails, wherein control group feed per ton adds manganous sulfate 200g, tests one group of feed per ton and adds threonine manganese 100g, two groups of feeds interpolation threonine manganese 200g per ton of test.Test-results sees Table 3.
Table 3: threonine manganese is to the influence of tilapia growth performance
Group First counterpoise g End counterpoise g Tail day weight gain g Feed coefficient Sickness rate %
Control group 42.93±0.98 a 95.53±0.50 a 1.75±0.04 a 1.45±0.02 a 13.25±1.23 a
Test one group 42.51±0.24 a 100.71±0.67 b 1.93±0.04 b 1.41±0.04 b 3.41±1.57 b
Test two groups 42.69±0.31 a 104.62±0.62 b 2.04±0.02 b 1.38±0.04 b 1.64±1.82 b
Annotate: same column shoulder marking-up parent phase expression difference together is remarkable (p>0.05) not; The female expression significant difference (p<0.05) inequality of same column shoulder marking-up.
As can be seen from Table 3, each group is there was no significant difference (p>0.05) between counterpoise just, but test group has the difference (p<0.05) of significance than control group on last counterpoise, tail day weight gain and feed coefficient index, but the test group differences is remarkable (p>0.05) not, and can effectively reduce the generation of sickness rate, difference reaches conspicuous level (p<0.05).Above test-results shows: in feed, add growth, reduction feed coefficient that threonine manganese can promote tilapia, and the generation that can improve immunizing power, reduction disease.

Claims (10)

1, a kind of name is called the Threonine huge legendary turtle compound of threonine manganese, and it is characterized in that: the molecular formula of described threonine manganese is:
Figure A2009100432980002C1
2, a kind of preparation method of threonine manganese as claimed in claim 1 may further comprise the steps:
(1) with the crystalline hydrate of the vitriol of the vitriol of manganese or manganese and mass concentration is 5%~30% Threonine aqueous solution, the crystalline hydrate of the vitriol of described manganese or the vitriol of manganese and the mol ratio of Threonine are (0.5~1.1): 2, under protection of inert gas, react, temperature of reaction is controlled at 60 ℃~100 ℃, pH value when interpolation sodium hydroxide is kept reaction is 4~8, obtains reaction product behind reaction 0.5~6h;
(2) described reaction product is carried out vacuum concentration until obtaining thick enriched material, perhaps obtain throw out, after more described enriched material or throw out being carried out drying, pulverizing, obtain the threonine manganese finished product with the moisture in the described reaction product of organic solvent extraction.
3, preparation method according to claim 2 is characterized in that described rare gas element is a nitrogen.
4, preparation method according to claim 2 is characterized in that in the described vacuum Concentrating Process, with vacuum degree control at 0.05~0.7kgf/cm 2, thickening temperature is controlled at 50 ℃~90 ℃, and concentration time is 0.5~4h.
5, preparation method according to claim 2 is characterized in that described organic solvent is ethanol, propyl alcohol or butanols, and the volume ratio of the reaction product of described organic solvent and its extraction is 4~12: 1, and the time of extraction is 2~30min.
6, preparation method according to claim 2 is characterized in that: described exsiccant method is to adopt air-flow wink-dry method or flash distillation wink-dry method, and drying temperature is 80 ℃~160 ℃.
7, a kind of as claimed in claim 1 or as the application in the preparation animal feedstuff additive of each prepares in the claim 2~6 threonine manganese.
8, application according to claim 7 is characterized in that: described threonine manganese is the fodder additives that is used to prepare pig feed, and the addition of described fodder additives is that pig feed per ton adds 100~200g.
9, application according to claim 7 is characterized in that: described threonine manganese is the fodder additives that is used to prepare poultry feed, and the addition of described fodder additives is that poultry feed per ton adds 300~400g.
10, application according to claim 7 is characterized in that: described threonine manganese is the fodder additives that is used to prepare aquatic animal, and the addition of described fodder additives is that aquatic animal feed per ton adds 100~200g.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111116438A (en) * 2019-12-25 2020-05-08 长沙兴嘉生物工程股份有限公司 Preparation method and application of manganese cystine

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101367745A (en) * 2008-10-20 2009-02-18 许昌元化生物科技有限公司 Novel preparation process for nano-aminophenol complex compound

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111116438A (en) * 2019-12-25 2020-05-08 长沙兴嘉生物工程股份有限公司 Preparation method and application of manganese cystine
CN111116438B (en) * 2019-12-25 2022-05-20 长沙兴嘉生物工程股份有限公司 Preparation method and application of manganese cystine

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